Benzothiazole azo compounds containing a dicarboximido radical



BENZOTHIAZOLE AZG C(EWOUNDS CGNTAIN- l lNG A DIQARBQXHMIDO RADICAL JamesM. Straley and David J. Wallace, Kingsport, Tenn, assignors to EastmanKodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing.Filed Oct. 22, 1962, Ser. No. 232,239

. 8 (Tlaims. (Cl. 260-158) This invention relates to novel compoundscontaining a dicarboximido radical, and more particularly to azocompounds, such as azo dyestuffs, containing a dicarboximido radical.Particular azo compounds containing this radical include compoundsobtained by coupling diazotized 2-amino benzothiazoles withdicarboximidoalkyl aniline coupling components such asN-[2(N-ethylm-toluidine ethyl] phthalimide.

These particular azo compounds have the general formula I 1 2 RN=NR1N-Rawherein R=a 2-benzothiazolyl radical, i.e.,

Ar NJ R =a hydrogen atom or lower alkyl group such as straight andbranch-chained lower alkyl groups including substituted lower alkylgroups, e.g., methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl;hydroxyalkyl, e.g., hydroxyethyl; cyanoalkyl, e.g., cyanoethyl;alkoxyalkyl, e.g., methoxyethyl; aryloxalkyl, e.g., phenoxyethyl;acyloxalkyl and haloalkyl; v

R =an alkylene radical straight or branch-chained, particularly loweralkylene, such as (CH wherein n is a positive integer from 1 to 4,

Z=a dicarboximido radical such as phthalimido, succinimido, maleimido,citraconimido, etc, as indicated in the table below, derived from thecorresponding anhydride.

The Z-aminobenzothiazoles which are diazotized and coupled with thementioned coupling components are, for example, 2-aminobenzothiazole,Z-amino-G-methylsulfonylbenzothiazole and other Z-aminobenzothiazolesdisclosed in the examples and table hereinafter.

The dicarboximidoalkyl aniline coupling components of the inventionwhich are coupled with the diazotized 2- aminobenzothiazoles, have thefollowing general formula II Ilia H-R1N-R3Z wherein R R R and Z have thesame meaning as given above and R is not substituted in the diazocoupling position.

United States Patent The dicarboirimido radical Z of the azo compoundsand coupling components of Formulas I and II above, has the followinggeneral formula wherein v Y represents the atoms necessary to complete aring containing 4 or 5 carbon atoms in addition to the nitrogen atoms,i.e., the hydrocarbon residue of the dicarboxylic acid anhydride fromwhich the radical is derived, including substtiuted and unsubstitutedalkylene, vinylene and ortho-phenylene groups such as ----CH; CH in thesuccinimido radical The dicarboximidoalkyl aniline coupling componentsare obtained as described in the following typical reaction by thecondensation of a dicarboxylic acid anhydride with aminoalkylanilines.

C Hs C J) Representative 5- and 6-membered cyclic dicarboximidoalkylaniline couplers referred to in the table and examples below useful forpreparing the azo compounds are N- [2 (N-ethyl-m-toluidine ethyl]phthalimide N- [2 N-ethylanilino) ethyl] succinimide N- [2(N-ethyl-m-toluidine ethyl] tetrachlorophthalimide V N- [2-(N-butyl-m-toluidine) ethyl] succinimide N- [2(N-etl1yl-m-toluidine)ethyl] bicyclo [2.2. 1 -5- heptene-2,3 -dicarb oximide N- [2(N-ethylanilino propyl] succinimide N- [2 (N-ethyl-m-toluidine) ethyl]cyclohexane- 1 ,Z-dicarboximide N- [2 (N-ethyl-rn-toluidine ethyl]citraconimide N-fl-glutarimidoethyl-N-ethyl-m-toluidineN-ethyl-N-succinimidomethylanilineNot-chloro-;3-hydroxypropyl-N-fl-succinimidoethyl-mtoluidineN-{S-acetoxyethyl-N-fi-succinimidoethyl-m-toluidine N -ethyl-N-phthalirnidomethyl-m-toluidine The azo compounds can be used for dyeingtextile materials including synthetic polymer filbers, yarns and fabricsgiving fast orange to violet shades when applied by con- Ventionaldyeing methods to polyester fibers. The azo compounds have moderateaffinity for cellulose ester and polyamide fibers and possess thevaluable property of staining wool less than do previous benzothiazoledyes. When the azo compounds are used for dyeing such hydrophobicmaterials, they should be free of Water-solubilizing groups. In generalthe dyes have 'good fastness, for example, to light, washing, gas(atmospheric fumes) and sublimation. The dyes are useful in applicationand discharge printing.

The following examples will serve to illustrate the preparation ofrepresentative intermediates and azo compounds of our invention.

EXAMPLE 1 (A) 89 g. (0.5 m.) of N-B-aminoethyl-N-ethyl-m-toluidine and74 g. (0.5 m.) of phthalic anhydride were mixed intimately and heatedgradually until an exothermic reaction began. The temperature rose to120 C. without further heating. After the temperature began to fall heatwas applied and held at 130-140 C. for 1 hour. The patrially cooled meltwas drowned in 500 cc. of hot ethyl alcohol and allowed to cool. Theproduct was filtered off, washed with a little alcohol and dried at 60C. The yield was 129 g. of material melting at 86-87 C. According toanalysis this product, N-[2(N-ethyl-m-toluidine)ethyl]phthalimide, hasthe structure (B) A coupler N-[2(N-ethyl-m-toluidine)ethyl]succinimidewas prepared as in A except that the anhydride] used was 50 g. (0.5 In.)of succinic anhydride and after the heating period the mix was drownedin 1 liter of water. Yield=99 g., melting at 81.5-82.5 C.

(C) 44.5 g. of the amine used in A and B, and 71.5 g. (0.25 m.) oftetrachlorophthalic anhydride were heated at 140-150 C. for about anhour, allowing the water formed to distill off. The mixture solidified,and after cooling, was pulverized and then recrystallized from 750 cc.of dimethyl formamide. The yellow solid was collected by filtration,washed with water, and dried at 100 C. The product melted at 1946 C. andanalysis showed it to be the tetrachloro derivative of the product of A,N- [2 (N-ethyl-m-toluidine) ethyl] tetrachlorophthalimide.

(D) 4-Carboxyphthalic anhydride was used as in A in place of phthalicanhydride to obtain the imide N-[2 N-ethyl-m-toluidine) ethyl]-4-carboxyphthalimide M.P. 160-162 C.

(E) 1,2,3,6-Tetrahydrophthalic anhydride was used as in A to produce theimide N-[2(N-ethyl-m-toluidine) ethyl]-1,2,3,6-tetrahydrophthalimideM.P. 76-77.5 C.

(F) 3-Nitrophthalic anhydride was used as in A to produce the imideN-B-3-nitrophthalimidoethyl-N-ethyl-mtoluidine M.P. 124-125 C.

(G) The compound of F was reduced using H and Raney nickel in alcohol toyield the aminophthalic acid imide N-{i-Baminophthalimidoethyl-N-ethyl-m-toluidine M.P. 116-117" C.

(H) 32.8 g. (0.2 m.) bicyclo[2.2.1]-S-heptene+2,3-dicarboxylic acidanhydride and 35.6 g. (0.2 m.) N-B- aminoethyl-N-ethyl-m-toluidine wereheated together at 130-140 C. for 1 hour. The melt was poured into 200cc. hot ethanol and allowed to cool over night. The solid was filteredoff, washed with ethanol and dried in air. The product N-[Z-(N-ethyl-m-toluidinel)ethyl]bicyclo[2.2.1]-5-heptene-2,3-dicarboximide melted at 7273.5 C.

(I) When the product of H is heated at 250-75 C. for min.cyclopentadiene is evolved forming N-B-maleimidoethyl-N-ethyl-m-toluidine.

(K) 77 g. (0.5 m.) cyclohexane-1,2-dicarboxy1ic anhydride was addedportionwise to 89 g. (0.5 m.) of N-fiamino-ethyl-N-ethyl-m-toluidine,the temperature rising spontaneously to 125 C. during addition, afterwhich the mix was heated 2 hours at 130-140 C. The viscous product N-[2- (N-ethyl-m-toluidine ethyl] cycl0hXa 4 2-dicarboximide was distilledcollecting the fraction. B. 183-4 C./.59 mm. N =1.5559.

(L) 32.8 g. (0.2 m.) N-fl-aminoethyl-N-ethyl-aniline and 20 g. succinicanhydride heated with 0.1 g. sulfanilic acid gave the fi-succinimidoderivative, M. 7072 C.

(M) N-B-aminoethyl-o-toluidine and succinic anhydride gave upon heatingthe corresponding imido compound, M. 131-2 C.

(N) 17.8 g. N-B-aminoethyl-N-ethyl-m-toluidine was added dropwise to11.2 g. citraconi'c anhydride. The mix was solid after addition wascomplete. The mix was heated 1 hour at l40-50 C. and distilled at 14650C./ 2.5 mm.

(0) N-B-aminoethyl-m-toluidine and succinic anhydride upon heating gavethe imido derivative melting at 162-5 C.

(P) The product of O was treated with ethylene oxide in ethanol to giveN-Z-hydroxyethyl-N-Z-succinimidoethyl-m-toluidine, M. -111 C.

(Q) 89.0 g. (0.5 m.) N-B-aminoethyl-N-ethyl-m-toluidine, 57.0 g. (0.5m.) of glutaric anhydride and 1 g. of sulfanilic acid were heated atISO- C. for 1.5 hours. Distillation in vacuo gave 79.6 g. ofN-B-glutarimidoethyl- N-ethyl-m-toluidine, B. 168-71 C./0.5 mm.

(R) 23.1 g. (0.1 m.) N-fi-succinimidoethyl-m-toluidine, 4.1 g. cupricacetate monohydrate, 0.1 g. hydroquine, and 58.3 g. (1.1 m.)acrylonitrile were heated at 80 C. for 24 hours and filtered hot. Uponcooling the product crystallized out, was filtered 0ft" andrecrystallized twice from ethanol, givingN-B-cyanoethyl-N-fl-succinimidoethyl-m-toluidine, M. 1214 C. Thestarting material was prepared by condensing succinic anhydride withN-B- aminoe thyl-m-toluidine at ISO-60 C. and pouring into ethanol.

(S) 19.8 g. of succinimide was stirred with 300 cc. of alcohol. Afteradding 19.6 cc. of 37% formaldehyde the mix was heated to reflux and27.8 g. of N-ethylaniline added. After 1 hours additional reflux thealcohol was distilled off and unchanged succinimide removed from theresidue by extraction with 200 cc. of 5% NaOH. The productN-ethyl-N-succinimidomethylaniline was washed with water and distilled,collecting the fraction boiling at 152-4 C./0.45 mm.

(T) 9.8 g. of 37% formaldehyde was stirred into 14.7 g. phthalimide in172 cc. of alcohol. The mix was brought to reflux and 15.3 g.N-ethyl-m-toluidine was added. After 30 min. further reflux the solutionwas chilled and the product isolated by filtration. Afterrecrystallization from alcohol the productN-ethyl-N-phthalimidomethyl-m-toluidine melted at 8082 C.

(U) The product of P was treated with acetic anhydride in acetic acid,drowned in water, filtered and air-dried to yieldN-,B-acetoxyethyl-N-fi-succinimidoethyl-m-toluidine.

(V) The product of O was treated in benzene with epichlorohydrin and thesolvent removed by distillation to yield N a chloro p hydroxypropylN-fi-succinimidoethyl-m-toluidinc.

EXAMPLE 2 Preparation of Dyes 6.84 g. (0.03 m.) of2-amino-6-methylsulfonylbenzothiazole were suspended in 72 cc. of waterand 42.8 cc. of 96% H 80 were added. The temperature rose and the aminedissolved completely. The solution was cooled to 5 C. and a solution of2.52 g. NaNO in 15.1 cc. of 96% H 80 was added in 20 min, keeping thetemperature below 0 C. After 1.75 hours stirring below 0 C. a clearbrown solution was obtained. This was run into a solution of 9.2 (0.03m.) of the product of Example 1A in 250 cc. of 15% H SO below 10 C. Dyeprecipitation began at once and the mix was diluted with 1 liter ofwater and the solid isolated by filtration, washing with water anddrying at 60 C. The dye so obtained imparts fast bluish red shades topolyester fibers.

The dye has the following formula l O 2 15 Li EXAMPLE 3 1 Example 2 wasrepeated using 4.5 g. of 2-aminobenzothiazole and 7.8 g. of the couplerof Example 1B. The

product imparts red shades to polyesters and somewhat bluer shades tocellulose acetate.

EXAMPLE 4 Example 2 was repeated using 6.2 g. of2-amino-6-thiocyanobenzothiazole and 9.7 g. of the imide of Example 1G.The dye imparts pink shades to polyester fibers.

EXAMPLE 5 Example 2 was repeated using 8.9 g. of N-ethyl-N-B-phthalimidoethylaniline. The product dyes polyesters in bright fastshades slightly yellower than does the product of Example 2.

EXAMPLE 6 EXAMPLE 9 Example 6 was repeated except the coupler used was 4The 7.8 g. of N-ethyl-N-p-succinimidoethyl-m-toluidine; product impartsfast red shades to polyester fibers.

EXAMPLE 10 EXAMPLE 11' 2.28 g. of 2- amino-6-methylsulfonylbenzothiaaolewas suspended in 24 cc. of water and 26.2 g. conc. H 804 added withstirring. The solution Was cooled to 5 C. and

V 0.84 g. NaNO in 9.3 g. conc. H 80 added below 0 C.

5 orasoz V 5/ After 2 hrs. the diaz'o solution was stirred into asolution of 2.32 g. of Nethyl-N-succinimidomethylaniline in 25 cc. of15% sulfuric acid in an ice-bath. After two hours in the ice-bath themix was drowned in Water, filtered, and the solid Washed Well with waterand air-dried. The product 4 (6 methylsulfonylbenzothiazole 2' azo)N-ethyl-N-succinimidomethylaniline dyes cellulose acetate and polyestersin bright scarlet shades.

The dyes described in the following table are prepared in the manner ofthe above examples using the indicated diazotized Z-aminobenzothiazolesand dicarboximidoalkyl aniline couplers wherein R R R and Z refer to thegeneral formulas above. For example, the first dye described in thetable is made by diazotizing 2-a'mino-6-methylsulfonylbenzothiazole andcoupling the product as described in Example 2 with Nv- [2(Nmethoxyethylaniline)ethyl] phthalimide. r

to obtain a dye having the formula Dicarboximidoalkyl aniline couplerColor of 2-Amlnobenzothiazole Polyester Diazotized Dyemgs 1 R2 -R3- Zfi-methylsullonyl mCHaC@Ha CzH5- OH2GHz Bicyclo[2,2,1]-5-h eptene- Pink.

2,3-dicarboxim1do. D m-OH3C6H3- CzH -CHzCH2 Tetraghlorophthal- D0.

Ill 0. Do -mCH3CsH3--. C2H5 CH2CHz Hexahydrophthalimido- Do. Do-mCH3C5H3- CzH5- CHQCH2 4earboxyphthahmido Do. Do mCH3O H3 C -CH2CH2-Citraconimido D0. D0 H CH2CHz Do..- -C2H4CN CH2CHz- Do..- C2H,OCHzCH2--- D0--- CH3 -CHzCH2-- D0.-. m-CH3CuHs-. -CH2CH2OOCCH3 -CH2CHz DomCH3CqH3 OH CHOH;C1 OH OHZ The azo compounds of the invention may beused for dyeing hydrophobic fibers such as linear polyester, celluloseester, acrylic, polyamide, etc., fibers in the manner described in US.Patents 2,880,050, 2,757,064, 2,782,187 and 3,043,827. The followingexamples illustrate methods by which the azo compounds of the inventioncan be used to dye polyester textile materials.

0.1 gram of the dye is dissolved in the dye pot by warming in 5 cc. ofethylene glycol monomethyl ether. A 2% Igepon T and 0.5% sodium ligninsulfonate aqueous solution is added, with stirring, until a fineemulsion is obtained. Water is then slowly added to a total volume of200 cc. 3 cc. of Dacronyx (a chlorinated benzene emulsion) are added andgrams of a textile fabric made of Kodel polyester fibers are entered.The fabric is worked 10 minutes without heat and then for 10 minutes at80 C. The dyebath is then brought to the boil and held at the boil forone hour. Following this, the fabric is rinsed in warm water, thenscoured in an aqueous 0.2% soap, 0.2% soda-ash solution. After scouring,the fabric is rinsed with water and dried. Accordingly, since the azocompounds of the invention are water-insoluble, they can be applied fromaqueous dispersions in the manner of the so-called dispersed dyes.However, coloration can also be effected, for example, by incorporatingthe azo compounds into the spinning dope and spinning the fiber asusual. The azo compounds of our invention have varying utility as dyes.The degree of utility varies, for example, depending upon the materialbeing dyed and the formula of the azo compound. Thus, for example, allthe dyes will not have the same degree of utility for the same material.

By cellulose aliphatic carboxylic acid esters having 2 to 4 carbon atomsin the acid groups thereof, we mean to include, for example, bothpartially hydrolyzed and unhydrolyzed cellulose acetate, cellulosepropionate and cellulose acetate-butyrate.

Polymeric linear polyester materials of the terephthalate type areillustrated of the liner aromatic polyester textile materials that canbe dyed with the new azo compounds of our invention. The terephthalatefibers sold under the trademarks Kodel, Dacron and Terylene, forexample, in the form of filaments, yarn and fabric, for example, areillustrative of the polyester textile materials that can be dyed. Kodelpolyester fibers are'more particularly described in US. Patent2,901,446. Dacron and Terylene polyester fibers are described, forexample, in U.S. Patent 2,465,319. The polymeric linear polyestermaterials disclosed in US. Patents 2,945,010, 2,957,745 and 2,989,363,for example, can be dyed. The linear aromatic polyester materialsspecifically named have a melting point of at least 200 C.

Nylon, in fiber, yarn and fabric form is representative of polyamideswhich can be dyed with the azo compounds.

The invention has been described in considerable detail With particularreference to certain preferred embodiscope of the invention as describedhereinabove, and as defined inv the appended claims.

What we claim is: 1. A20 compounds having the general formula 2RN=NR1N-R3- Z wherein R=a 2-benzothiazolyl radical,

R =a monocyclic aromatic radical,

R =a member of the .class consisting of hydrogen, alkyl, hydroxyalkyl,phenoxyalkyl, acyloxyalkyl, haloalkyl and cyanoalkyl, the alkyl groupsof which are lower alkyl,

R =lower alkylene and Z=a dicarboximido radical, said compounds beingfree of water-solubilizing groups.

2. A20 compounds having the formula R=a 2-benzothiazolyl radical,

R =a monocyclic aromatic radical,

R =lower alkyl,

Z=a succinimido radical, said compounds being free ofwater-solubiliz-ing groups.

3. A20 compounds having the formula R=a 2-benzothiazolyl radical,

R =a monocyclic aromatic radical,

R =l0wer alkyl,

Z=a phathalimido radical, said compounds being free ofwater-solubilizing groups.

4. An azo compound having the formula 5. An azo compound having theformula CHZCHZN s cm 9 10 6. An azo compound having the formula 8. Anazo compound having the formula N N 02115 c c H o a B l1 \ON=N-- N/L-CH,

CN--N N\ -CH: 5 OZN N0- H3 OHzOH9N N 63120112N\ L c- H, f

7. An azo compound having the formula 3 i;lgg gliifigs gziglzg {0,11, 32,771,466 Towne et a1 Nov; 20, 1956 2,852,504 Towne et a1 Sept. 16, 1958CNCH OHSO O 15 3,037,993 Shulgin June 5, 1962 B40112 1 3,043,647 Kopp eta1. July 10, 1962 C-CH; 3,060,191 Kolb et a1 Oct. 23, 1962 I 3,068,056Coe Dec. 11, 1962 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIONPatent No. 3,161,631 December 15, 1964 James M. Straley et a1.

It is hereby certified that'error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 1, lines 31 and 52, for "alklsulfonyl" read alkylsulfonyl column4, line 26, for "hydroquine" read hydroquino e column 9, lines 12 to 18for that portion of the formula reading:

column 10, lines 2 to 7, the formula should appear as shown belowinstead of as in the patent:

C H O N H r GN/ CCH OZYFKIS/C N 2 Signed and sealed this 24th day ofAugust 1965.

(SEAL) Attest:

ERNEST W. SWIDER I EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. AZO COMPOUNDS HAVING THE GENERAL FORMULA